Collisional activation of N2O decomposition and CO oxidation reactions on isolated rhodium clusters.
Collisional activation of N2O decomposition and CO oxidation reactions on isolated rhodium clusters.
复制标题
DOI：
10.1021/jp405267p
复制
发表时间：
2013-09
期刊：
影响因子：
--
通讯作者：
I. S. Parry;A. Kartouzian;S. M. Hamilton;O. Balaj;M. Beyer;S. Mackenzie
中科院分区：
文献类型：
--
作者：
I. S. Parry;A. Kartouzian;S. M. Hamilton;O. Balaj;M. Beyer;S. Mackenzie
用傅里叶变换离子回旋共振质谱研究了N2 O修饰的铑原子簇RhnN 2 O（+）（n = 5，6）的反应。碰撞诱导的解离与Ar显示，导致两个过程之一;解吸的完整的N2 O部分（表示在母体簇中的分子吸附）或N2 O分解释放分子氮与后者在更高的碰撞能量变得越来越占主导地位。与早期采用红外激发的研究结果一致[爱马仕，A. C.的;等人J. Phys. Chem. Lett. 2011，2，3053]，观察到Rh 5 ON 2 O（+）与Rh 5 N2 O（+）的性质不同，其中一氧化二氮的分解主导前者的化学。在其他实验中，RhnN 2 O（+）团簇与CO的反应性进行了研究。计算了（13）CO的化学吸附量为存款ca. 2 eV的能量注入到母团簇中，在团簇表面引发一系列化学过程，这些过程符合简单的反应机理。在Rh 5 N2 O（+）和Rh 6 N2 O（+）母簇离子的反应分支比中再次观察到明显的差异。对于n = 5的簇合物，N2 O还原/CO氧化是最重要的反应通道，而n = 6的簇合物则优先氧化为Rh 6 O（+），同时损失N2和CO.所有研究的结果都讨论了红外驱动的过程中相同的父集群物种[汉密尔顿，S。M.;等.美国化学会志2010，132，1448;物理化学杂志A，2011，115，2489]。
The reactions of nitrous oxide decorated rhodium clusters, RhnN2O(+) (n = 5, 6), have been studied by Fourier transform ion cyclotron resonance mass spectrometry. Collision induced dissociation with Ar is shown to lead to one of two processes; desorption of the intact N2O moiety (indicating molecular adsorption in the parent cluster) or N2O decomposition liberating molecular nitrogen with the latter becoming increasingly dominant at higher collision energies. Consistent with the results of earlier studies, which employed infrared excitation [Hermes, A. C.; et al. J. Phys. Chem. Lett. 2011, 2, 3053], Rh5ON2O(+) is observed to behave qualitatively differently to Rh5N2O(+) with decomposition of the nitrous oxide dominating the chemistry of the former. In other experiments, the reactivity of RhnN2O(+) clusters with CO has been studied. Chemisorption of (13)CO is calculated to deposit ca. 2 eV into the parent cluster, initiating a range of chemical processes on the cluster surface, which are fit to a simple reaction mechanism. Clear differences are again observed in the reaction branching ratios for Rh5N2O(+) and Rh6N2O(+) parent cluster ions. For the n = 5 cluster, the combined N2O reduction/CO oxidation is the most significant reaction channel, while the n = 6 cluster preferentially is oxidized to Rh6O(+) with loss of N2 and CO. Even larger differences are observed in the reactions of the N2O decorated cluster oxides, RhnON2O(+), for which more reaction possibilities arise. The results of all studies are discussed in relation to infrared driven processes on the same parent cluster species [Hamilton, S. M.; et al. J. Am. Chem. Soc. 2010, 132, 1448; J. Phys. Chem. A, 2011, 115, 2489].